CN106000468A - Metalloporphyrin-inorganic crystal composite microspheres and preparation method thereof - Google Patents
Metalloporphyrin-inorganic crystal composite microspheres and preparation method thereof Download PDFInfo
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- CN106000468A CN106000468A CN201610387498.0A CN201610387498A CN106000468A CN 106000468 A CN106000468 A CN 106000468A CN 201610387498 A CN201610387498 A CN 201610387498A CN 106000468 A CN106000468 A CN 106000468A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention discloses metalloporphyrin-inorganic crystal composite microspheres and a preparation method thereof. The metalloporphyrin-inorganic crystal composite microspheres are composed of a metal ion and metalloporphyrin with the mass ratio of (0.1-5):1. An immobilization method of single metalloporphyrin or multiple metalloporphyrins has the advantages of simple operation, low cost and the like. The stability of the metalloporphyrin in the prepared metalloporphyrin-inorganic crystal composite microspheres is improved, and the activity of the metalloporphyrin basically remains unchanged or is increased to some extent; the prepared metalloporphyrin-inorganic crystal composite microspheres make a metalloporphyrin catalytic reaction become a non-homogeneous reaction from a homogeneous reaction, so that the metalloporphyrin is easily separated and recovered from a reaction system, the reuse rate of the metalloporphyrin is improved, and the utilization rate of the metalloporphyrin is improved. The characteristics make the metalloporphyrin-inorganic crystal composite microspheres have great application prospects in the fields of metalloporphyrin catalytic oxidation, biological sensing and the like.
Description
Technical field
The present invention relates to metalloporphyrin technical field, specifically, relate to a kind of metalloporphyrin-mineral crystal complex microsphere
And preparation method thereof.
Background technology
Metalloporphyrin is as a kind of bionic catalyst, because it has high selectivity, high activity and reaction condition gentleness etc.
Feature, catalyst is respectively provided with good catalytic performance to reaction, and reaction condition is gentle, simple to operate, easy and carrying capacity of environment
Little, there is potential application prospect, metalloporphyrin is again a homogeneous catalyst, and homogeneous catalyst disadvantage is difficult to from instead
Answer and system separates and recovers and reuses.
The supported of homogeneous catalyst can overcome homogeneous catalyst to reclaim the problems such as difficult, is the outer catalytic field of Present Domestic
A popular research topic, exploitation application in once make breakthroughs, will facilitate catalytic production industry the newest
Revolution.
Summary of the invention
It is an object of the invention to the technical deficiency overcoming existing catalysis of metalloporphyrin agent to be not easily recycled and separate, it is provided that a kind of
Metalloporphyrin-mineral crystal complex microsphere and preparation method thereof.
For realizing the purpose of the present invention, be the technical scheme is that
A kind of metalloporphyrin-mineral crystal complex microsphere, is made up of with metalloporphyrin metal ion, and its mass ratio is 0.1
～5:1.
In above-mentioned metalloporphyrin-mineral crystal complex microsphere, the structural formula of described metalloporphyrin is:
M=:Zn, Mn (II), Cu (II), Co, Sn, Fe (II), V (II), Mg, Ni (II)
R1、R2、R3、R4:-H,
R5、R6: H, SO3 -, Cl, NO2, CH3, CH2CH3
In above-mentioned metalloporphyrin-mineral crystal complex microsphere, the molecular weight of described metalloporphyrin is preferably 300-3000.
In above-mentioned metalloporphyrin-mineral crystal complex microsphere, described metal ion be copper ion, calcium ion, magnesium ion,
One in iron ion, ferrous ion, barium ions, zinc ion or bivalent nickel ion.
The preparation method of above-mentioned metalloporphyrin-mineral crystal complex microsphere, comprises the steps:
Metalloporphyrin is dissolved in solvent, metal ion is dissolved in the water, metalloporphyrin solution addition phosphoric acid is delayed
Rush in liquid, add metal ion solution, under static conditions, at a temperature of 0～50 DEG C, obtain metalloporphyrin-mineral crystal
Complex microsphere.
In above-mentioned preparation method: described solvent is water, ethylene glycol, dimethyl sulfoxide, methanol, N, N-dimethyl formyl
One in amine, aniline, ethanol, acetone, acetonitrile, pyridine or isopropanol.
In above-mentioned preparation method: described phosphate buffer includes dihydrogen phosphate and hydrogen phosphate；Dihydrogen phosphate
It is 1～1000mM with the concentration of phosphoric acid hydrogen two；In the mixed liquor that described metalloporphyrin and described phosphate buffer form,
The concentration of described metalloporphyrin is 0.01mg～10mg mL-1；The pH of phosphate buffer is 5.0～9.0.
Compared with prior art, there is advantages that the present invention provide a kind of single metalloporphyrin or
The process for fixation of various metals porphyrin, the method has the advantages such as simple to operate, with low cost.The gold that the present invention prepares
Belonging to the stability of metalloporphyrin in porphyrin-mineral crystal complex microsphere to be improved, the activity of metalloporphyrin is held essentially constant
Or increasing, prepared metalloporphyrin-mineral crystal complex microsphere makes the catalytic reaction of metalloporphyrin by being contrary
Inhomogeneous reaction should be become so that metalloporphyrin is easy to separate from reaction system and reclaim, and improves metalloporphyrin
Repeat usage, improves the utilization rate of metalloporphyrin.Above feature makes this kind of metalloporphyrin-mineral crystal complex microsphere exist
There is great application prospect in the fields such as catalysis of metalloporphyrin oxidation, bio-sensing.
Accompanying drawing explanation
Fig. 1 is XRD and the standard card of cupric phosphate crystal and metalloporphyrin-cupric phosphate crystal complex microsphere in embodiment 1
Comparison diagram.
Fig. 2 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 1-cupric phosphate crystal complex microsphere.
Fig. 3 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 2-cupric phosphate crystal complex microsphere.
Fig. 4 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 3-cupric phosphate crystal complex microsphere.
Fig. 5 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 4-cupric phosphate crystal complex microsphere.
Fig. 6 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 5-cupric phosphate crystal complex microsphere.
Fig. 7 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 6-cupric phosphate crystal complex microsphere.
Fig. 8 is the scanning electron microscope (SEM) photograph of the metalloporphyrin prepared by embodiment 7-cupric phosphate crystal complex microsphere.
Fig. 9 is the conversion of the metalloporphyrin prepared by embodiment 1-cupric phosphate crystal complex microsphere catalysis epoxidation of cyclohexene
Rate and selective relation curve.
Figure 10 is urging of the metalloporphyrin prepared by embodiment 1-cupric phosphate crystal complex microsphere catalysis epoxidation of cyclohexene
The repeat performance figure of agent.
Detailed description of the invention
Experimental technique shown in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
The formula of PBS (pH=7.4): 10mM HPO4 2-,2mM H2PO4 -, 137mM NaCl and 2.7mM KCl.
The activity of metalloporphyrin in following embodiment:
Load capacity L of following embodiment metalloporphyrin is obtained by the following formula:
w1=(C1-C2)×V
Wherein W1And W2Represent quality (mg) and the metalloporphyrin-inorganic compounding of the metalloporphyrin being carried on microsphere respectively
Microsphere gross mass (mg), C1And C2The concentration (mg/mL) of the metalloporphyrin in solution before and after expression forms microsphere respectively, V represents to be made
With the cumulative volume (mL) of metalloporphyrin solution.
The concentration of metalloporphyrin solution all uses ultraviolet-visual spectrometer to be measured.
Embodiment 1, the preparation of meso-tetra-(4-N-pyridine radicals) Cob altporphyrin (CoTPyP)-cupric phosphate crystal complex microsphere:
1. preparing metal porphyrin concentration is the N,N-dimethylformamide solution of CoTPyP and the phosphate of 0.3mg/mL
The copper sulphate pentahydrate aqueous solution of buffer solution and 200mM.
2. take the phosphate buffer 20mL prepared in step 1 in beaker, add the CoTPyP in 5mL step 1 molten
Liquid, mix homogeneously, add the copper-bath in 1mL step 1, in 25 DEG C of incubators, after mix homogeneously, stand 72h.
3. collecting precipitation after being filtered by the mixture of step 2 gained, be washed with deionized 3 times, it is heavy to be again collected by filtration
Forming sediment, vacuum drying 4h i.e. obtains meso-tetra-(4-N-pyridine radicals) Cob altporphyrin-cupric phosphate crystal complex microsphere.
The thing phase composition of complex microsphere prepared by the present embodiment by X-ray diffraction (XRD) characterize and with corresponding crystal mark
Quasi-card is compared, as it is shown in figure 1, metalloporphyrin load microsphere is basic with the microsphere analyzed pattern not having metalloporphyrin to load
Unanimously, and and Cu3(PO4)2·3H2The standard card coupling of O, it was demonstrated that the mineral crystal of microsphere consists of Copper phosphate (Cu3(PO4)2) trihydrate.
The scanning electron microscope (SEM) photograph of the complex microsphere prepared in the present embodiment as in figure 2 it is shown, as shown in Figure 2, complex microsphere
Particle diameter be about 4 μm, in complex microsphere prepared by the present embodiment, the load capacity of metalloporphyrin is 8%.
Embodiment 2～3, meso-tetra-(4-N-pyridine radicals) copper porphyrin-cupric phosphate crystal complex microsphere and meso-tetra-(4-N-
Pyridine radicals) preparation of manganoporphyrin-cupric phosphate crystal complex microsphere:
Respectively meso-tetra-(4-N-pyridine radicals) Cob altporphyrin in embodiment 1 preparation process 1 is replaced with meso-tetra-(4-
N-pyridine radicals) copper porphyrin-cupric phosphate and meso-tetra-(4-N-pyridine radicals) manganoporphyrin-cupric phosphate, other operating procedures are identical.
The scanning electron microscope (SEM) photograph of meso-tetra-(4-N-pyridine radicals) copper porphyrin-cupric phosphate crystal complex microsphere as it is shown on figure 3, by
Fig. 3 understands, and the particle diameter of complex microsphere is about 4 μm.The load capacity of the metalloporphyrin in crystal complex microsphere is 8%.
The scanning electron microscope (SEM) photograph of meso-tetra-(4-N-pyridine radicals) manganoporphyrin-cupric phosphate crystal complex microsphere as shown in Figure 4, by
Fig. 4 understands, and the particle diameter of complex microsphere is about 4 μm.The load capacity of the metalloporphyrin in crystal complex microsphere is 8%.
The preparation of embodiment 4, meso-cobalt tetraphenylporphyrin (CoTPP)-cupric phosphate crystal complex microsphere:
1. preparing metal porphyrin concentration be the methanol solution of CoTPP of 0.3mg/mL and phosphate buffered solution and
The copper sulphate pentahydrate aqueous solution of 200mM.
2. take the phosphate buffer 20mL prepared in step 1 in beaker, add the CoTPP in 5mL step 1 molten
Liquid, mix homogeneously, add the copper-bath in 1mL step 1, in 25 DEG C of incubators, after mix homogeneously, stand 24h.
3. collecting precipitation after being filtered by the mixture of step 2 gained, be washed with deionized 3 times, it is heavy to be again collected by filtration
Forming sediment, vacuum drying 4h i.e. obtains meso-cobalt tetraphenylporphyrin-cupric phosphate crystal complex microsphere.
As it is shown in figure 5, as shown in Figure 5, the particle diameter of complex microsphere is about for the scanning electron microscope of complex microsphere prepared by the present embodiment
It is 4 μm.The load capacity of the metalloporphyrin in complex microsphere prepared by the present embodiment is 8%.
Embodiment 5～6, meso-tetraphenyltin porphyrin (SnTPP)-cupric phosphate and meso-tetraphenyl manganoporphyrin (MnTPP)-
The preparation of cupric phosphate crystal complex microsphere:
Respectively the meso-cobalt tetraphenylporphyrin in embodiment 5 preparation process is replaced with meso-tetraphenyltin porphyrin and
Meso-tetraphenyl manganoporphyrin, other operating procedures are identical.
The scanning electron microscope (SEM) photograph of meso-cobalt tetraphenylporphyrin-cupric phosphate crystal complex microsphere as shown in Figure 6, it will be appreciated from fig. 6 that
The particle diameter of complex microsphere is about 4 μm.The load of the metalloporphyrin in meso-cobalt tetraphenylporphyrin-cupric phosphate crystal complex microsphere
Amount is 8%.
The scanning electron microscope (SEM) photograph of meso-tetraphenyl manganoporphyrin-cupric phosphate crystal complex microsphere as it is shown in fig. 7, as shown in Figure 7,
The particle diameter of complex microsphere is about 4 μm.The load of the metalloporphyrin in meso-tetraphenyl manganoporphyrin-cupric phosphate crystal complex microsphere
Amount is 8%.
Embodiment 7, meso-tetra--(4-phenylbenzimidazole sulfonic acid base) Cob altporphyrin (CoTPPS)-meso-cobalt tetraphenylporphyrin-cupric phosphate
The preparation of crystal complex microsphere:
1. preparing metal porphyrin concentration be the methanol solution of CoTPP and CoTPPS of 0.3mg/mL and phosphate-buffered molten
The copper sulphate pentahydrate aqueous solution of liquid and 200mM.
2. take the phosphate buffer 20mL prepared in step 1 in beaker, add the CoTPP in 2.5mL step 1 and
CoTPPS solution, mix homogeneously, add the copper-bath in 1mL step 1, stand in 25 DEG C of incubators after mix homogeneously
24h。
3. collecting precipitation after being filtered by the mixture of step 2 gained, be washed with deionized 3 times, it is heavy to be again collected by filtration
Forming sediment, it is multiple that vacuum drying 4h i.e. obtains meso-cobalt tetraphenylporphyrin-meso-four-(4-phenylbenzimidazole sulfonic acid base) Cob altporphyrin-cupric phosphate crystal
Close microsphere
As shown in Figure 8, as shown in Figure 8, the particle diameter of complex microsphere is about for the scanning electron microscope of complex microsphere prepared by the present embodiment
It is 4 μm.The load capacity of the metalloporphyrin in complex microsphere prepared by the present embodiment is 8%.
The activity of enzyme and stability and the detection to cyclohexene in metalloporphyrin-mineral crystal complex microsphere:
The assay method of the activity of metalloporphyrin: in order to verify the activity of metalloporphyrin, the present embodiment pair in complex microsphere
The activity of the complex microsphere system that embodiment 1 prepares gained is determined.
By measuring complex microsphere and free metal porphyrin respectively to the conversion ratio of cyclohexene and selective relation curve,
Compare the activity of metalloporphyrin by calculating the concrete reactivity parameter of metalloporphyrin, concrete operation step is as follows: claim respectively
Take in the flask that the metalloporphyrin complex microsphere prepared in 50mg embodiment 1 adds different 25mL with free metal porphyrin, add
Entering in 4mmol cyclohexene, add 20mmol isobutylaldehyde, add 10ml 1,2-methylene chloride as solvent is passed through oxygen, Mei Geban
Hour sampling, uses gas chromatograph for determination conversion ratio and selectivity, and experimental result is as it is shown in figure 9, as shown in Figure 9, compound micro-
Ball is compared with free metal porphyrin, and the activity of metalloporphyrin improves about 10%.
The assay method of metalloporphyrin stability: in order to verify the stability of metalloporphyrin in complex microsphere, the present invention examines
Examine the repeat performance of complex microsphere.Concrete operation step is as follows: be combined by the metalloporphyrin of preparation in 50mg embodiment 1
Microsphere, joins in 4mmol cyclohexene, adds 20mmol isobutylaldehyde, is passed through oxygen, reacts 4h, uses gas chromatograph for determination
Conversion ratio and selectivity, reclaim complex microsphere catalyst, repeat above-mentioned experimental procedure, i.e. obtain the reusability of complex microsphere
Can figure.
Claims (7)
1. metalloporphyrin-mineral crystal complex microsphere, it is characterised in that be made up of with metalloporphyrin metal ion, its quality
Ratio is 0.1～5:1.
Metalloporphyrin the most according to claim 1-mineral crystal complex microsphere, it is characterised in that: described metalloporphyrin
Structural formula is:
M=:Zn, Mn (II), Cu (II), Co, Sn, Fe (II), V (II), Mg, Ni (II)
R1、R2、R3、R4:-H,
R5、R6: H, SO3 -, Cl, NO2, CH3, CH2CH3。
Metalloporphyrin the most according to claim 1-mineral crystal complex microsphere, it is characterised in that: described metalloporphyrin
Molecular weight is 300-3000.
Metalloporphyrin the most according to claim 1-mineral crystal complex microsphere, it is characterised in that: described metal ion is
One in copper ion, calcium ion, magnesium ion, iron ion, ferrous ion, barium ions, zinc ion or bivalent nickel ion.
5. the preparation method of metalloporphyrin described in claim 1-mineral crystal complex microsphere, it is characterised in that include walking as follows
Rapid:
Metalloporphyrin is dissolved in solvent, metal ion is dissolved in the water, metalloporphyrin solution is added phosphate buffer
In, add metal ion solution, under static conditions, at a temperature of 0～50 DEG C, obtain metalloporphyrin-mineral crystal be combined
Microsphere.
Preparation method the most according to claim 5, it is characterised in that: described solvent be water, ethylene glycol, dimethyl sulfoxide,
One in methanol, N,N-dimethylformamide, aniline, ethanol, acetone, acetonitrile, pyridine or isopropanol.
Preparation method the most according to claim 5, it is characterised in that: described phosphate buffer include dihydrogen phosphate and
Hydrogen phosphate；The concentration of dihydrogen phosphate and phosphoric acid hydrogen two is 1～1000mM；Described metalloporphyrin delays with described phosphate
Rushing in the mixed liquor of liquid composition, the concentration of described metalloporphyrin is 0.01mg～10mg mL-1；The pH of phosphate buffer is 5.0
～9.0.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405131A (en) * | 2002-10-29 | 2003-03-26 | 郭灿城 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN1521153A (en) * | 2003-02-08 | 2004-08-18 | 湖南大学 | Process for preparing aldehyde and alcohol by selective catalysis air oxidation of toluene and substituted toluene |
| WO2010019976A2 (en) * | 2008-08-19 | 2010-02-25 | Universität Innsbruck | Porphyrins and metalloporphyrins |
| CN101972677A (en) * | 2010-09-30 | 2011-02-16 | 广西大学 | Preparation method of nano zinc oxide supported metalloporphyrin catalyst and application thereof to catalytic oxidation of toluol |
| CN105457682A (en) * | 2015-11-13 | 2016-04-06 | 广西大学 | Preparation method and catalytic application of lead sulfide immobilized tetra (pentafluorophenyl) metalloporphyrin |
-
2016
- 2016-06-01 CN CN201610387498.0A patent/CN106000468B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405131A (en) * | 2002-10-29 | 2003-03-26 | 郭灿城 | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin |
| CN1521153A (en) * | 2003-02-08 | 2004-08-18 | 湖南大学 | Process for preparing aldehyde and alcohol by selective catalysis air oxidation of toluene and substituted toluene |
| WO2010019976A2 (en) * | 2008-08-19 | 2010-02-25 | Universität Innsbruck | Porphyrins and metalloporphyrins |
| CN101972677A (en) * | 2010-09-30 | 2011-02-16 | 广西大学 | Preparation method of nano zinc oxide supported metalloporphyrin catalyst and application thereof to catalytic oxidation of toluol |
| CN105457682A (en) * | 2015-11-13 | 2016-04-06 | 广西大学 | Preparation method and catalytic application of lead sulfide immobilized tetra (pentafluorophenyl) metalloporphyrin |
Non-Patent Citations (1)
| Title |
|---|
| JUN GE, ET AL: "Protein-inorganic hybrid nanoflwers", 《NATURE NANOTECHNOLOGY》 * |
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